Perfluoroalkyl group containing alpha,beta-unsaturated di-and triesters and polymers thereof

ABSTRACT

PERFLUOROALKYL GROUP CONTAINING ESTERS OF A,B-UNSATURATED DI- AND TRIESTERS AND POLYMERS THEREOF ARE DISCLOSED. THE POLYMERS HAVE SOIL REPELLENT PROPERTIES PARTCULARLY IF APPLIED TO SUBSTRATES SUCH AS TEXTILE PAPER, LEATHER AND THE LIKE. THE ESTERS ARE DERIVED FROM ETHER AND/OR CARBON-CARBON DOUBLE BOND CONTANING PERFLUOROALCOHOLS OR MERCAPTANS AND A,N-UNSATURATED DI- OR TRIACIDS.

United States Patent Ofifice 3,794,623 Patented Feb. 26, 1974 US. Cl.260--78.4 E 26 Claims ABSTRACT OF THE DISCLOSURE Perfluoroalkyl groupcontaining esters of afi-unsaturated diand triesters and polymersthereof are disclosed. The polymers have soil repellent propertiesparticularly if applied to substrates such as textile paper, leather andthe like. The esters are derived from ether and/ or carbon-carbon doublebond containing perfiuoro- I alcohols or mercaptans and:,[3-111'1S8t11l3tfid dior triacids.

RELATED APPLICATION This application is a continuation-in-part ofcopending application Ser. No. 720,370, filed Apr. 10, 1968.

SUMMARY OF THE INVENTION This invention is directed to novel monomersand polymers which can be prepared from them. The disclosed polymerspossess low free surface energies and therefore soil repellentproperties as evidenced by their oil and water repellency. The polymersare useful especially as coatings for a wide variety of substratesincluding textiles, paper, leather, painted wood and metallic surfaceand the like.

The novel monomeric compounds are c p-unsaturated diand triesters of thefollowing formula:

wherein R R R are hydrogen, methyl, R A or R ACH with the proviso thatat least one or two of the R-substituents represent R,A or R,ACH

RIA IS RrXC F CII CHC Hz OC H: O R, is C F wherein q is 3 to 18 andpreferably 6 to 12; m is 1 to 12 and preferably 2, 3 or 4; n is 2 to 12and preferably 2, 3 or 4; p is 2 to 6 or zero; X is oxygen or zero if pis zero.

In the disclosed ego-unsaturated diand triesters, the R A group willcontain at least one ether or one carboncarbon double dond or acombination of ether and carhon-carbon double bond linkages. Fromstructure I, it is apparent the ether linkage if present may be in theperfluorinated segment (R OC F or in the nonfluorinated segment ('C I-IOC H or CH=CHC H OC H If R R and R represent the substituents as definedabove, structure I represents the following esters:

Type ester R R R Fumarate H -ARi --H -AP-i -H H H A R! CH:

AR! -'H CH: Itaeonatan. H H CHzAR-I Methylene malonate H H AR;cis-Aconitate H AR: CHzARi trans-Aconitate AR: H CHzARI If monomers oftype I are homoor copolymen'zed, polymers are obtained containing; thefollowing repeating units or moieties:

F i f1 L 1's 1d wherein RgA, R R R are as defined above.

DETAILED DESCRIPTION OF THE INVENTION Several alternate techniques existfor the preparation of the a,fl-diand triesters of the formula:

wherein R A, R, R and R have been previously defined. The perfiuoroalkyl(R A) monomers of type I can be derived from R, alcohols or R,mercaptans of the type:

and fumaric, maleic, mesaconic, citraconic, itaconic, methylene malonic,aconitic (cis and trans) acids as well as the acid chlorides or acidanhydrides, if obtainable, or esters of these acids. In the abovealcohols and mercaptans, R;, X, p, m and n maintain the definition foundin conjunction with the novel monomer of Formula I.

As has been mentioned the novel monomers of Formula I are obtained fromthe alcohols and mercaptans of types III to VII and the listed acid,acid chlorides, acid anhydrides or esters of these acids. Well-knownesterification or transesterification procedures may be employed. Sincemany of the acids have high melting points or poor solu bilitycharacteristics, it usually is preferable to employ the acid chlorides,anhydrides or lower alkyl esters of the listed acids. It is alsopossible and often advantageous to employ lower alkyl esters of the R,alcohols of types III and V to VII for transesterification reactionsinstead of the alcohol itself.

Another alternative synthesis for the monomers of Formula I where RA isn 11,0 C F; C H2mOC- is the reaction of a perfiuoroalkyl iodide,

(VIII) R,oc F ,,c H I :CHCOCI), trans 2R1CH=CHCmH2mOH v :(CHC O OCmHZmCH CHRI), trans CHCO O 2RrCH=CHCmHz OC Hz OH CHCO I CH COOCnHmOCmHmll :(CHCOOCIL), trans 2R1CmHzmOCnH1nOCCH;

zonoooonmno CmHZmRI) trans lCHCOOH). trans N(C2Hs)t ZRIOC FzDCmHmHI zcnooocmnmc rz om). trans A detailed disclosure for the starting R,alcohols, esters of these alcohols, R -mercaptans and R, iodides oftypes III through VIII exists in the following patents:

Alcohols IV, US. 3,088,849; V, US. 3,285,975; III, US.

3,293,306; Italian Pat. 804,233; German Often. 1,915,- 609; French Pat.1,574,801.

Reference is made to these teachings for suitable starting compoundsuseful for preparation of the novel monomers of type I disclosed herein.

From the standpoint of illustration, several different classes ofreactions are provided to demonstrate the preparation of the startingcompounds of types III to VII which are useful to form the novelperfluoroalkyl a,;3-un saturated diand triesters of Formula I:

l base 2R1O C IIi CI'IlCIIiO II ABN RII CHz=CHCmHmOH R1CH1CIIICmII OIItom RICII=CIIC mHzmo II A B N=azobisisobuty ronitrilo V Rd IICECCmILmOHRt'CII C1Cm1I2mOII R1CII:CIICmIIgmOI-I 1hI+ CI[2 011GmIIQmOC IIB OIIRtCIi CIIICmHgmOCnIIhOH I OH- VII R1CH=CIICmH2mOCnHmOH lHz, Pd/C VIntcincmcmugmo CnHhO II Reduction RICmHQmOC HmCOOCIhRtCmII2mOCnII:nCII;OH

The perfiuoroalkyl containing esters of type I are useful in thepreparation of polymers of type II. These polymers are characterized bythe fact that each monomer moiety in the polymer chain contains a closepacked pair or triplet of R -groups in contrast to the analogous R-acrylate or methacrylate polymers which contain just one R group permonomer moiety as the following examples demonstrate:

The polymers containing this closeness of spacing or packing of the Rgroup have been found to possess lower free surface energies overanalogous R; aorylate or methacrylate polymers which contain only one Rgroup per monomer moiety.

Monomers of type II of the present disclosure can be utilized for thesynthesis of graft polymers due to the fact that these monomers show areduced tendency to homopolymerize but an increased tendency towardgraft ing reactions in comparison to analogous R acrylates andmethacrylates.

Generally polymerization may be by bulk, solution, suspension oremulsion techniques. Solution and emulsion procedures are preferred.

Inemulsion polymerization, the monomer or monomers to be polymerized areemulsifide together in a water solution of a surface active agent to agiven monomer concentration of from about 5% to about 50%. Usually thetemperature is raised to between 40 C. and 70 C.. to effectpolymerization in the presence of an added catalyst. A suitable catalystmay be any one of the commonly known agents for initiating thepolymerizafi'im. of 3111 ethylenically unsaturated compound. Theconcentration of the catalyst for the polymerization is usually between0.1% and 2% based upon the weight of the monomers.

Suitable surfactants or emulsifying agents include cationic, anionic ornon-ionic types. Since the cationic and nonionic types can be used inmost textile treating baths, they are preferred. The hydrophobic portionof the surfactant may be hydrocarbon or'fluorinated hydrocarbon.

Suitable surfactants that may be used include, for example, non-ionicsurfactants in which the hydrophilic group is a poly (ethoxy) group andthe hydrophobic portion is either a hydrocarbon or a fluorocarbon groupsuch as the ethylene oxide condensates of alkyl phenols, alkanols,alkylamines, alkyl thiols, alkylcarboxylic acids, fluoroalkyl carboxylicacids, fluoroalkyl amides and the like.

Suitable cationic surfactants include for example quaternary ammoniumsalts or amine salts containing at least one long chain alkyl,fluoroalkyl, or high alkyl substituted benzene or naphthalene group toprovide the hydrophobic portion.

Polymerization is preferably carried out for a reaction period adjustedto obtain essentially quantitative conversion of the fluorinatedmonomer. The optimum reaction time will depend upon the catalyst usedand the polymerization temperature and other conditions, but willgenerally be in the range of from 0.5 to 24 hours.

The polymerization temperature will depend upon the catalyst chosen. Inthe case of emulsion polymerization in aqueous media, it will generallybe in the range of from to 90 C. The polymerization is generally mostconveniently and preferably carried out at atmospheric pressure whereverpossible.

In solution polymerization, the monomer or monomers are dissolved in asuitable solvent such as fluorinated s01- vents, for example,hexafiuoroxylene, trifluorotoluene or mixtures thereof with acetoneand/or ethylacetate and polymerized in a reaction vessel usinginitiators such as azobisisobutyronitrile or other azo initiators atconcentrations of 0.1% to 2.0% at 40 100 C. under nitrogen.

As mentioned, besides homopolymers, valuable copolymers are obtained bypolymerization of the foregoing novel perfluorinated monomers with otherpolymerizable monomers having ethylene unsaturation.

Examples of suitable comonomers are alkyl vinylethers, such as methylvinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, 2-methoxyethyl vinyl ether, n-propyl vinyl ether, t-butyl vinyl ether, isoamylvinyl ether, n-hexyl vinyl ether, Z-ethylbutyl vinyl ether,diisopropylrnethyl vinyl ether, l-methyl-heptyl vinyl ether, n-decylvinyl ether, n-tetradecyl vinyl ether, and n-octadecyl vinyl ether.

Propylene, butylene and isobutylene are preferred a-olefins useful ascomonomers with the novel fiuoro monomers of the present invention.Straight and branched chain a-olefins are useful with up to 18 carbonatoms in the side chain.

Useful copolymers of the novel perfluorinated compounds of the inventionare formed with vinyl esters, e.g. vinyl acetate, vinyl esters ofsubstituted acids, such as for example, vinyl methoxyacetate, vinyltrimethylacetate, vinyl isobutyrate, isopropenyl butyrate, vinyllactate, vinyl caprylate, vinyl pelargonate, vinyl myristate, vinyloleate and vinyl linoleate; vinyl esters of aromatic acids, such asvinyl benzoate.

Also useful as comonomers are styrene and related monomers whichcopolymerize readily with the novel esters of this invention such aso-methylstyrene, p-methylstyrene, 3,4-dim'ethyl styrene, 2,4,6-trimethylstyrene, m-ethyl styrene, 2,5-diethyl styrene.

Additional useful comonomers are ethylene and chlorofluoroandcyano-derivatives of ethylene such as vinyl chloride, vinyidenechloride, vinyl fluoride, vinylidene fiuoride, acrylonitrile,methacrylonitrile, tetrafluoroethylene,

trifluorochloroethylene, hexafiuoropropylene; acrylate and methacrylatemonomers, particularly those with 1 to 12 or 18 carbon atoms in theester groups such as n-propyl methacrylate, Z-methyl cyclohexylmethacrylate, methyl methacrylate, t-butyl methacrylate, n-butylmethacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butylacrylate, butyl acrylate, 3-methyl-1-pentyl acrylate, octyl acrylate,tetradecyl acrylate, s-butyl acrylate, 2-ethy1hexyl acrylate, 2methoxyethyl acrylate, and phenyl acrylate; dienes particularly1,3-butadiene, isoprene, and chloroprene, 2 fiuoro butadiene, 1,1,3trifiuoro butadiene, 1,1,2,3 tetrafiuoro butadiene, 1,1,2 trifluoro3,4-dichlorobutadiene and triand pentafiuoro butadiene and isoprene;nitrogen-vinyl monomers such as vinyl pyridine, N-vinylimides, vinylsuccinimide, vinyl pyrolidone, N- vinyl carbazole and the like.

Also useful as comonomers with some of the novel monomers of the presentinvention are vinyl monomers which contain perfiuorinated side chains.Examples of such perfluorinated monomers are vinyl ethers of the typedisclosed in US. 2,732,370 and US. 2,828,025; vinyl esters containingfluorinated alkyl groups disclosed in U.S. 2,592,069 and US. 2,436,144.Other useful monomers are acrylates and methacrylates and derivativesthereof such as those disclosed in U.S. 2,628,958; US. 3,256,230; US.2,839,513; U.S. 3,282,905; US. 3,252,932; and US. 3,304,278.

Other R; groups containing monomers useful for copolymerization arefumarates, maleates, itaconates, and other eunsaturated diand triestersas described in the copending application Ser. No. 199,793 and thefollowing applications assigned to the assignee of the presentinvention: Ser. No. 720,370, filed Apr. 10, 1968, in the names of EduardK. Kleiner and Martin Knell; Ser. No. 732,040, filed May 27, 1968, inthe names of Eduard K. Kleiner, Martin Knell and Pier Luigi Pacini; Ser.No. 812,439, filed Apr. 1, 1969, in the name of Eduard K. Kleiner; Ser.No. 820,647, filed Apr. 30, 1969, in the name of Eduard K. Kleiner; andSer. No. 833,606, filed June 16, 1969, in the names Eduard K. Kleinerand Pier Luigi Pacini.

As mentioned, it may also be desirable to include a minor amount ofreactive comonomers in order to improve the wash and dry-cleanproperties of the novel tetxile finishes obtained according to thepractice of this invention. Such monomers act as cross-linking agentsduring the curing operation. Such reactive comonomers are generallyemployed in amounts of 0.1% to 2%.

Other reactive monomers which may be included are by way ofillustration: acrylic acid, methacrylic acid, acrylamide,methacrylamide, N-methylolacrylamide, 2- hydroxyethyl methacrylate oracrylate, hydroxypropyl acrylates or methacrylates, t-butylaminoethylmethacrylate, and glycidyl methylate. Of the foregoing,N-methylolacrylamide and Z-hydroxyethyl methacrylate are preferred.

Coatings of the homopolymers and copolymers according to the presentinvention can be prepared and applied from solvent solutions or fromaqueous emulsions. Suitable solvents are fluoroalkanes,fiuorochloroalkanes, fluoroalkyl substituted aromatics, alkyl esters ofpertinent:- alkanoic acids, chlorinated alkanes or aromatics,hydrocarbon aromatics, ketones, esters and ethers. Especially useful assolvents are the fluorinated liquids, and especiallya,a,a-trifluorotoluene, otherwise known as benzotrifluoride,hexafluoroxylene and mixtures of these with ethyl acetate or acetone andthe like. Concentrations of the fluorinated polymers of the presentinvention in solvent to provide coatings with eifective oil and waterrepellency properties will generally be of the order of 0.01 to 10% andpreferably from 0.1 to 2.0% by weight. Blends of the emulsions of thepolymers of this invention with blended emulsions of other polymers andcopolymers are particularly useful in textile finishes. The polymers andcopolymers are generally of a non-fluorinated type; however, asindicated below other fluorinated polymers and copolymers may be used ifdesired. Non-fluorinated polymers useful in such blends, include forexample, but without limitation, polymers and copolymers of alkylacrylates and alkyl methacrylates, such as methyl methacrylate, ethylmethacrylate, hexyl methacrylate, and n-octyl methacrylate. Aparticularly suitable polymer is poly-n-octyl methacrylate. Also usefulare polymers and copolymers of acrylic acid, methacrylic acid, styrene,alkyl styrene, butadiene, 2 methyl -1,3 butadiene, 2 chloro 1,3butadiene; polymers and copolymers of vinyl esters such as vinylacetate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl 2 ethylhexanoate; polymers and copolymers of vinyl halides and vinylidenehalides, such as vinyl chloride, vinylidene chloride, vinyl fluoride,vinylidene fluoride; polymers and copolymers of allyl esters such asallyl propionate, or allyl caprylate; polymers and copolymers of vinylketones, such as vinyl methyl ketone, vinyl ethyl ketone, and the like;polymers and copolymers of vinyl ethers such as methyl vinyl ether,cetyl vinyl ether, and the like; polymers and copolymers of acrylamide,methacrylamide, N-methylol acrylamide, N methylol methacrylamide,N-isopropyl acrylamide, and acrylonitrile and methacrylonitrile.

In the formation of the polymers disclosed herein it is mostadvantageous and desirable in the RA group to keep the specific alkylenelinkages m and n as small as possible. Longer alkylene linkage groupstend to increase the free surface energies of polymers of type II.

The selection of the linkage groups between R, and the polymerizabledouble bond of the diand triacids depend largely on the desired solidstate properties of polymer of type II. Substitution of an alkylenelinkage of the type -C H with a more flexible alkylene-O-alkylenelinkage of the type -C H OC H or a stiffer carboncarbon double bondlinkage of the type -C=C changes the solid state properties of a polymerof type II. By selecting a certain linkage group it is thereforepossible to tailor a polymer of type II with desired solid-stateproperties. Softeness and hardness of a polymer (so-called hand) is animportant factor for polymers which are utilized as textile finishes.

The polymers of this disclosure possess desirable soil repellencyproperties. A useful manner of measuring the relative ratings of thepolymers is by oil and water repellency ratings. In the examples thefollowing test procedures were used:

The AATCC Oil Rating was determined according to Standard Test Method118-1966T of the American Association of Textile Chemists and Colorists.Ratings are given from (minimum) to 8 (maximum). A commonly acceptedlevel on soil repellency fabrics in the U5. is an oil repellency of 4.

Another oil repellency method is the 3-M Oil Test procedure of Grajekand Peterson, Textile Research Journal, April 1962, p. 323.

The AATCC water spray test rating was determined according to StandardTest Method 22-1966 of the American Association of Textile Chemists andColorists XXXVII, 1961, p. 1952 (also designated ASTM D-583- 58).Ratings are given from 0 (minimum) to 100 (maximum).

The polymers in the examples were applied to polyestercotton (65/ 35%)at a concentration to yield 0.2% fluorine based on the weight of thefabric.

To further illustrate the innovative aspects of the present inventionthe following examples are provided.

EXAMPLE A 4-perfluoroheptyl-3-buten-1ol, cis and trans,

(a) Addition of perfluoroheptyl iodide, C7F15I, to 3- butyn-l-ol,I-ICECCH CH OH.Perfluoroheptyl iodide (99.2 g., 0.200 mole) 3-btuyn-1-ol(redistilled Farchan Chem., B.P. 78 (99 mm.), 11 1.4390, 14.0 g., 0.200

mole) and ABN (0.654 g., 4.00 10 mole) were charged to a Fischer-Porteraerosol pressure tube, cooled to 78, evacuated to 0.55 mm. and filledwith nitrogen three times and sealed. The tube was heated for 15.5 hr.at 700. Unreacted materials were removed by distillation, B.P. 41 (28mm.), 21 1.3340, 15.9 g., heating the flask to 119. The residual oil99.2 g., 88% conversion, solidified when cooled to room temperature. AnIR spectrum showed vOH 3360, vC-=C 1640 cmf The residue was distilled ina short path still, B.P. (0.05 mm.) (bath 104-124), 95.2 g., leavingonly a few drops of residue. NMR analysis showed proton resonances at 62.31, singlet, OH group; 6 2.9, triplet, CH CI-I OH; 6 3.8, triplet, CHCH OH; and 6 6.47, triplet, CF CH=CICH These data were consistent forstructure of cis and trans C F CH:CICH CH OH.

Analysis.Calcd. for C H F IO (percent): C, 23.34; H, 1.07; F, 50.35; I,22.42. Found (percent): C, 23.61; H, 1.16; F, 50.59; I, 22.45.

(b) Zinc reduction of 4-perfluoroheptyl-3-iodo-3- buten-l-ol, C FCH=CICH CH OH.-4-perfluoroheptyl- 3-iodo-3-buten-1-ol (89.2 g., 0.157mole) was. added in portions to a rapidly stirred slurry of zinc (26.0g., 0.40 g.-atom, 30 mesh, Bakers analyzed) in anhydrous ethanol (400ml.) while introducing hydrogen chloride gas from a cylinder. Thereaction flask was fitted with a reflux condenser, paddle stirrer andgas inlet tube extending to one inch above the level of the stirredliquid, and heated to reflux temperature (78). In 1.5 hrs. the zinc wasgone and 10 g. additional zinc was added; after 2 hrs. this wasrepeated. Foaming occurred during the reaction and the flow of hydrogenchloride was regulated to maintain reaction of the zinc. After 6 hrs.the reaction flask was set up for distillation and ethanol (-350 ml.)removed up to internal temperature. The residual brown oil was pouredinto 500 ml. of water, extracted 3 times with CCL, (50 ml.) and theextracts rinsed with aqueous sodium sulfite soln. The organic layer wasdried (MgSO filtered and distilled in a 24-inch platinum spinning bandcolumn. Fractions taken were: I, B.P. 104107 (14 mm.), n 1.3420, 10.9g.; II, 111 (15 mm.), 11 1.3393, 25.1 g.; III, -109 (14 mm.), 12 1.3392,20.0 g.; IV, 88-82 (3.2-2.5 mm.), 11 1.3421, 2.5 g. A dark brown residueof 4.0 g. remained. The combined fractions amounted to 85% recovery of98.9% purity according to gas chromatographic analysis. The structurewas confirmed by NMR analysis which gave 6 2.52, protons of OH and =CCH6 3.7, CH OH; 6 5.2-6.7, CH=CH.

Analysis.-Calc. for C I-1 C 0 (percent): C, 30.01; H, 1.60; F, 64.75.Found (percent): C, 30.38; H, 1.62; F, 64.50.

EXAMPLE B 4-perfluorobutyl-3-buten-l-ol, cis and trans, C F CH=CHCH CHOH (a) Addition of perfluorobutyl iodide, C F I, to 3- butyn-l-ol,HCECCH CH OH.-Perfluorobutyl iodide (Thiokol Chem. Corp., redistilled,B.P. 68, 69.2 g., 0.0210 mole), 3-butyne-1-ol (Farchan Lab., 14.0 g.,0.200 mole) and ABN (0.656 g., 4.00 mmoles) were charged to aFischer-Porter aerosol fiat-bottomed tube cooled to 78, evacuated andfilled with nitrogen 3 times and sealed. The tube was stirred by amagnet bar in an oil bath set at 70.0" C. for 26 hr. Distillation of theorange liquid (83.0 g.) in a two-ft. platinum spinning band column gavethe following fractions: 1, B.P. 36/9.0 mm., 11 1.4383, 1.25 g.(3-butyne-1-ol); II-IV, B.P. 7884/2.5-3.5 mm., 11 1.4139; 64.94 g.

plus 2.5 g. residue in the distillation flask. The conversion to C,FCH=CI(CH OH was 78%; total conversion to 9 distilled products was 85%.An IR spectrum showed 113500-3100, vCH 3050, vCH 2930, 2880, VC=C 1630;vCH 1350; IICF, 1250-1130; bands at 1050, 980 (w.), 930 (w.), 880, 740,695, 590 and 520 cmr Analysis.-Calcd. for C H F IO (percent): C, 23.08;H, 1.45; F, 41.08; I, 30.49. Found (percent): C, 23.12; H, 1.47; F,40.90; I, 30.68.

(b) Zinc reduction of 4-perfluorobutyl-3-buten-1-01, C F CH=CICH CHOH.Ethanol (anhydrous, 300 ml.) was saturated with hydrogen chloride(Matheson, anhydrous from cylinder) while stirring at 72. Zinc powderg., 0.15 g.-atom, 30 mesh) and (64.0 g., 0.153 mole) were added. Themixture foamed and turned colorless as additional portions of zincpowder 10 g., 0.15 g.-atom, 60-200 mesh) were added over a one hourperiod at 80. After 4 hrs. the flask was set up for downwarddistillation heated with steam, and 200 ml. of ethanol was removed; thebrown oil residue was poured into 200 ml. of water and extracted withbenzene (2x 50 ml.), and ether (50 ml.). The organic extract was rinsedwith aqueous bisulfite solution, dried over MgSO and distilled in a2-ft., platinum spinning band column. C FCH=CH(CHZ)2OH, B.P. 93/30 mm.,n 1.3453 was collected in 3 fractions; 39.2 g. (88%). A hold-up fraction(1.15 g.) was stripped from the column also, 12 1.3474 (total yield91%). A residue (1.30 g.) remained. An infrared spectrum of the productshowed vOH 3500-3100, vC=C 1665; and bands at 1050, 975, 925, 880, 865,745 and 690 cmf Analysis.-Calc. for CBHIFQO (percent): C, 33.11; H,2.43; F, 58.94. Found (percent): C, 33.22; H, 2.56; F, 59.09.

EXAMPLE C 3-perfiuoroheptyl-2-propen-l-ol, cis and trans, C F CH=CHCH OH(a) Addition of perfluoroheptyl iodide, C F I, to 2- propyn 1 o1, HCECCHOH.--Perfluoroheptyl iodide (81.0 g., 0.163 mole), 2-propyn-1-ol(redistilled Aldrich, B.P. 112, n 1.4301, 9.2 g., 0.163 mole) and ABN(0.656 g., 400x10- mole) were charged to a fiat bottom Fischer-Porteraerosol tube, stirred by a magnet bar. The tube was cooled to -78,evacuated and filled with nitrogen and sealed. The reaction mixture was.heated to 70.0 C. in an oil bath and the two layers stirred rapidly topromote reaction. After 1.5 hr. the mixture had become homogeneous.Heating was continued for a total of 18.5 hr., and the orange liquiddistilled. in variable take off still (no column). A mixture ofperfiuoroheptyl iodide and 2-propyn-1-ol (39.8 g.) was recovered, B.P./42 mm. The adduct C 1 CH=CICH OH distilled at B.P. 91-98 (1.5-2.2 mm.),11 1.3863, 43.0 g. (48% conversion) leaving a residue of 3.4 g. Theproduct solidified at room temperature. An infrared spectrum (KBr)showed vCH 2400-2300, VC=C 1640; bands at 990, 890, 835, 815, 740, 735,720, 650 and 530 cmf An NMR spectrum was consistent. The olefinicprotons gave a complex pattern at 5 6.1-7.2, the methylene protonsappeared at 5 4.3 and the excangeable OH at 3.2.

Analysis.-Calc. for C H F IO (percent): C, 21.75; H, 0.73; F, 51.63; I,22.99. Found (percent): C, 21.77; H, 0.86; F, 51.45; I, 22.54.

(b) Zinc reduction of 3 perfiuoroheptyl-2-iodo-2- propen-l-ol, C FCH=CICH OH.--3-perfluoroheptyl-2- iodo-Z-propen-l-ol (93.6 g., 0.170mole), ethanol (500 ml.) and zinc (30 mesh, 30.0 g., 0.46 g.-atom) washeated to 82 and stirred rapidly while saturating with hydrogenchloride. After 2 hr., zinc (10.0 g., 0.153 g. atom) was added andreaction continued for 2 hr. Ethanol (400 ml.) was distilled from thereaction mixture. On standing overnight the colorless liquid turnedyellow. It was poured into 300 ml. of water and extracted with ether(150 ml., ml.), with dichloromethane (50 ml.

twice), rinsed with aqueous sodium bisulfite and dried (MgSO An IRspectrum (salt plates) of sample 1 showed VOH 3500-3200, PCH 3050, 2980,2930 and 2860, 2 sharp bands vC=C=C 2000 and 1960 cmf 11C=C (d.)1780-1760, heavy CF bands and bands at 1020, 980, 965, 880, 855, 830,785, 730, 715, 695, 655, 640 CIHSI. These data indicate than an allenicsubstance was present in the reaction mixture which decomposed onattempted distillation. Distillation in the Z-ft. platinum spinning bandcolumn gave evidence of decomposition in the pot liquid (turned darkred). Fractions collected: I, B.P. 32/18 mm., r2 1.3670, 0.75 g., II toIV, B.P. 94-98/13 mm., n 1.3311, 38.9 g., and distillation residue, 21.5g. The combined fractions II to IV were washed with 10 ml. of aqueousbisulfite solution, extracted into ether, dried (MgSO and redistilled ina spinning band column. A fraction, B.P. 93-95 10 mm., 11, 1.3305, 31.6g. was obtained. The NMR showed 6 1.99, a singlet, OH; 6 4.37, amultiplet, CH 6 5.2-6.8; multiplet CH=CH; these data are consistent withthe structure of C F CH=CHCH OH.

Analysis.Calc. for C HsF O (percent): C, 28.18; H, 1.18; F, 66.88. Found(percent): C, 28.24; H, 1.28; F. 66.25.

EXAMPLE D 1 l-per fiuoroheptyl- 1 O-undecenl-ol, cis and trans, C F CH=CH (CH 0H (a) Addition of perfluoroheptyl iodide, C F I, to 10-undecen-l-ol, CH =CH(CH OH.C F I (100 g., 0.200 mole), IO-undecen-l-ol(34.5 g., 0.202 mole) and ABN (0.990 g., 0.00600 mole) were charged to aflatbottom 250 ml. Fisher-Porter aerosol bottle, cooled to -78,evacuated and filled with nitrogen 3 times. The mixture was heated in anoil bath at 70.0 C. while stirring with a magnet bar in the bottle for17 hr. The colorless, slightly cloudy liquid was pumped down to 0.30 mm.while heating to 116 to remove any unreacted C F I (trap liquid, 3.0 g.,11 1.3760). The residual oil, 130.6 g. was distilled in a variabletakeoff head (no column) A forerun, 4.24 g., n 1.4125 and c n cn cnncnpon B.P. 129-132/0.l5 mm., n 1.4101, 101.2 g. distilled, leaving aresidue (6.0 g.). Infrared spectrum showed: uOH 3330, VCH 2930, 2850,aCH 1470, 1440, 1360, 1330; heavy CF bands at 1240-1150; bands at 990,890, 840, 810, 740, 722, 712, 705, 665 and 640 cmf NMR showed: 61.2-2.2, 16 protons, multiplet (CI-1 6 2.23, 1 proton, singlet, OH; 62.4-3.4, 2 protons, multiplet OF CH CHI; b 3.71, 2 protons triplet, CHOH; 5 4.43, 1 proton 5 lines, CH -CH-CH These data were consistent forstructure C F CH CHI(CH 0H.

Analysis.Ca1C. for C H F IO (percent): C, 32.45; H, 3.33; F, 42.78; I,19.05. Found (percent): C, 32.90; H, 3.49; F, 42.50; I, 22.68.

(b) Dehydrohalogenation of 11-perfluoroheptyl-10 iodo undecan-l-ol, C FCI-l CHI(CH OH.-ll-perfluoroheptyl-lO-iodo-undecan-l-ol (110 g., 0.165mole), was dissolved in ethanol (100 m1.) and added to a rapidly stirredsolution of KOH (11.2 g., 0.200 mole) in 100 ml. of aqueous ethanol. Thetemperature rose from 30 to 37 as the yellow color faded, and themixture became foamy. After 23 hr., at 37", ethanol was removed bydistillation in a 6-inch packed column. The oil and separated salt wasmixed with ml. of water, extracted with 100, 50 and 25 ml. of ether andwith 25 ml. of benzene, dried over MgSO, and distilled in a three ft.spinning band column. A forerun was yellow in color, B.P. 112-114/0.25mm., n 1.3809, 4.0 g.; the products B.P. 113/0.21 mm., n 1.3766 and1.3761, 49.1 and 28.3 g. was collected in two fractions; leaving aresidue, 3.5 g. Yield of was 91.5% of theory. An infrared spectrumshowed: vOH 3330, uCH 2930, 2850; vC=C 1670; heavy CF bands at1250-1150; and bands at 1095, 1055, 1020, 1008, 970, 870, 820, 790, 725,720, 700, 680 cm. The fractions Were combined, treated with activatedcarbon to remove yellow color, rinsed with ether and redistilled in thespinning band column. A forerun, B.P. 100-132/ 1.0 mm., 2.05 g., ayellow oil was again obtained; suc ceeding fractions were almostcolorless. The final fraction, B.P. 112/0.22 mm., 11 1.3755, 54.5 g. wassubmitted for analysis. The NMR showed: 6 1.32, 14 protons, broadsinglet, (CH 6 1.54, 1 proton, sharp singlet, OH; 8 2.2, 2 protons,broad multiplet, C:C-CH 6 3.63, 2 protons, triplet CH OH; 6 5.0-6.8, 2protons, multiplet, CH=CH. These data are consistent with the postulatedstructure.

Analysis.Calc. for C H F O (percent): C, 40.15; H, 3.93; F, 52.94. Found(percent): C, 40.10; H, 3.95; 'F, 53.08.

EXAMPLE E 1l-Perfiuoroisopropyb10-undecen-1-ol, cis and trans, (CFCFCH=-CH(CH )OH (a) Addition of perfiuoroisopropyl iodide. (CF CPI, toIO-undecen-l-ol, CH =CH(CH OH.A Fischer- Porter aerosol tube was chargedwith ABN (0.656 g., 4.00 mmoles), 10-undecen-1-ol (34.1 g., 0.200 mole,Aldrich 99%) and perfluoroisopropyl iodide (62.5 g., 0.210 mole,) cooledto -78, evacuated and filled 3 times with nitrogen and sealed. Thereaction tube was heated at 70 for 26 hr. and the colorless liquid (95.4g.) was transferred to a flask and distilled in a variable take-off headwithout column. A forerun, B.P. 102-112/0.40 mm., 1.4398, 1.2 g. wasremoved, and three fractions of (CF CFCH CHI (CH OH were collected. Asmall amount (6.0 g.) of the very volatile (CF CFI collected in the DryIce trap. The total distilled products amounted to a 91% yield. Aninfrared spectrum of the sample showed vOH 3500-3100, vCI-I 2930, 2950,BCH 1460, 1430, 1370, 1340; VCF 1300-1210, 1150; and bands at 1110,1060-1040, 950, 770, 728, 615, 540 and 510 cm.-

Analysis.Calc. for C H F IO (percent): C, 36.06; H, 4.76; F, 28.53; I,27.22. Found (percent): C, 36.19; H, 4.76; F, 28.62; I, 27.28.

(b) Dehydrohalogenation of 11-perfiuoroisopropyl-10- iodo-undecan 1 ol,(CF CFCH CHI(CH OH. Potassium hydroxide (11.2 g., 0.200 mole) wasdissolved in 59 ml. of water, 200 ml. of ethanol added and the solutionstirred by magnet bar as (79.4 g., 0.170 mole), was added at 35. Ayellow color appeared initially and disappeared in a few minutes. Thesolution was kept at 35 while stirring for 15.5 hr., poured into 100 ml.of water and the aqueous layer extracted with 100, 50 and 30 ml. ofether, using salt to assist in separating the layers in the firstextraction. The combined orange-colored organic fraction was extractedwith aqueous sodium bisulfite, rinsed with benzene, dried over MgSO andpassed over activated alumina to remove color and polar impurities. Theproduct mixture was distilled in a variable takeoff head without acolumn: I, B.P. 109- 1ll/2.2 mm., 11 1.3986, 28.1 g.; II, B.P. 115-116/2.4 mm., n 1.3964, 17.9 g.; III, B.P. 108-109/1.50 mm., 11 1.3964, 7.5g.; total recovery of (CF CFCH: CH (CH H 53.3 g., 94% yield. An infraredspectrum showed VOH 3500-3100; vCH 2930, 2850; 11C=C 1670; 6CH 1460,1440, rCF 1300-1200, 1180; bands at 1050, 980, 740, .720, 710 and 535cmf The combined fractions I, II and III Were redistilled in anadiabatic spinning band column at B.P. 78-82 C./0.1 mm. The NMR showed:6 1.32, 14

protons, broad singlet, (CH 6 1.72, 1 proton, sharp singlet, OH; 6 2.18,2 protons, broad multiplet,

6 3.6, 2 protons, triplet CH OH; 5 5-6.8, 2 protons, multiplet, CH=CH.These data are consistent with the structure of (CF CFCH:CH(CH OH.

AnaIysis.-Calc. for C14H21Fq0 (percent): C, 49.70; H, 6.25; F, 39.31.Found (percent): C, 50.61; H, 6.37; F, 39.11.

EXAMPLE F 6-perfluoroheptyl-3-oxa-5-hexen-1-ol, cis and trans, C FCH=CHCH OCH CH OH (a) Addition of perfluoroheptyl iodide, C F I, to B-allyloxyethanol, CH :CHCH OCH CH OH.Perfluoroheptyl iodide (165 g.,0.334 mole), fl-allyloxyethanol (34.4 g., 0.334 mole, B.P. 63 (16 mm.),11 1.4329) and ABN (ABN, 2,2775 g., 0.0134 mole) were charged to aFischer-Porter aerosol pressure tube, cooled to -78, evacuated to 0.55mm. and filled with nitrogen three times and sealed. The tube was heatedin a bath at 700 for 22 hr. The yellow liquid (201.2 g.) was distilledfrom an oil bath in a short path still, B.P. 100 (0.15 mm.), n 1.3914,175.7 g., and B.P. 101 (0.18 mm.), n 1.3924, 2.6 g. A black residue of8.8 g. remained. The trap liquid (11.8 g., 11 1.3309) was principallyrecovered C F I. The conversion to5-iodo-6-pentadecafluoroheptyl-3-oxahexan-l-ol C F CH CHICH OCH CH OH,was and the yield (b) Dehydrohalogenation of 6-perfluorohepty1-5-iodo-3-oxahexan 1 o1, C F CH CHICH OCH CH OH.-6-perfiuoroheptyl-5-iodo-3-oxahexan-1-ol (90.0 g., 0.150 mole) was addedto a stirred solution of KOH (11.2 g., 0.200 mole) in 250 ml. of 60%aqueous ethanol, kept at 35 for 12 hr. and allowed to stand 3 days. Thecolorless solution was distilled, at reduced pressure to remove ethanol(225 ml.). Water ml. was added to the residue, and extracted 3 timeswith ether (50 ml.). The combined ether extracts were dried (MgSO anddistilled. 6-pentadecafiuoroheptyl-3-oxa-5-hexenol,

B.P. 98-100 (1.5 mm.), 11 1.3490, 65.2 g. (93%) was collected in 3fractions of constant B.P. and refractive index. A residue of 2.8 g.remained. An infrared spectrum (KBr, liquid film) showed vOH 3600-3300,vCH 2930 and 2860, 11C=C 1680, BCH 1470, 1450 and 1360, vCF 1260-1200,1150 and bands at 1030, 985, 965, 890, 840, 805, 735, 708, 700, 660, 640and 530 cm. The bands 1680, 985, 965 and 890 are associated with the RCH=CH group. The 3 fractions were combined and redistilled in a 3-ft.stainless steel spinning band column, B.P. 96/ 1.4 to 85/0.80 mm. NMRshowed: 6 2.82, singlet, OH; 6 3.61, multiplet, OCH CH OH; 8 4.17, =CHCHO; and 6 5.5- 6.7, multiplet C-H=CH. These data were consistent forstructure C F CH=CHCH OCH CH OH.

Analysis.-Calc. for C H F O (percent): C, 30.65; F, 60.61; H, 1.93.Found (percent): C, 31.10; F, 60.00; H, 2.10.

EXAMPLE G 6-perfiuoroheptyl-3-oxahexan-1-ol,

C F CH CI-I CH OCH CH OH Catalytic hydrogenation of6-perfiuoroheptyl-5-iodo-3- oxahexan-l-ol, (ExampleF(a)).6-perfluoroheptyl-5-iodo-3-oxahexan 1 01 (59.8 g., 0.100 mole),potassium hydroxide (8.4 g., 0.15 mole) dissolved in methanol ml.) and5% palladium on carbon (Matheson, 'Coleman and Bell) (4.0 g.) werecharged to a Parr hydrogenation bottle, and the mixture shaken at 32-35for 14.5 hr. at 40 p.s.i. The pressure dropped from 40 to 35.5 p.s.i. in10 min.; when re-pressured to 45 p.s.i., the pressure dropped to 40p.s.i. in 1 hr.,

and remained unchanged. The drop in pressure corre-v sponded to 0.11mole of hydrogen. The mixture was filtered, methanol removed bydistillation, water (100 ml.) added to the slurry and product extractedinto ether (50 ml. three times). The combined extracts were dried (MgSOand distilled in a 24-inch platinum spinning band column. The firstfraction was yellow, B.P. 8894 (1.1 mm.). 11 1.3451, 3985 g. FractionII, B1. 94 (1.0 mm.), n 1.3443, 12.0 g. was slightly yellow, and fraction HI, B.P. 95 (1.0 mm.), n 1.3430, 24.57 g., was almost colorless.The total recovery of was 85%. A residue of 1.4 g. remained. An IRspectrum (KBr, liquid lfilm) showed vOI-I 3400, uCH 2950, 2880; ECH1450, 1360, z/CF 12801150; bands at 9'85, 890, 835, 805, 745, 720, 710,700, 655, 565, and 540 cmi- The bands at 1675 and 965 in the unsaturatedcompound were absent in the product NMR showed: 1.6-2.9, multiplet, CFCH CH CH O; 5 3.55, multiplet, CH 'OCH CH OH; 6 2.95 (or 2.48) 0Hexchangeable proton. These data were consistent for structureAnalysis.-Calc. for C H F O (percent): C, 30.52; H, 2.35; F, 60.35.Found (percent): C, 30.49; H, 2.27; F, 60.24.

EXAMPLE H 4-perfluoroisoprop oxy- 1 1,2,2-tetrahydroperfluorobutylacetate, 0 CHzO O 4-perfluoroisopropoxy 1,1,2,2tetrahydroperofiuorobutyl iodide, (CF CFOCF CF CH CH I (35.2 g. 0.080mole, prepared according GC-547, Example 2), cadminrn oxide (10.25 g.,0.080 mole) and glacial acetic acid (140 g.) were charged into amagnetically stirred stainless steel autoclave. The autoclave wassealed, then heated to 180182 C. (inside temperature) for 20 hours. Thereaction mixture was then added to 300 ml. of water. 2 layers wereobtained; they were separated and retained. The lower organic layer wasdistilled through a Vigreaux column. The product (18.0 g.) was obtainedat 99102 C./9095 mm. Hg and was shown by VPC to be pure. The upperaqueous layer was then extracted with 50 ml. of chloroform. The extractwas washed successively with sodium bicarbonate, then water, and wasthen dried over sodium sulfate. The chloroform layer was then combinedwith the residue of the above mentioned distillation, the solvent wasdistilled ofl? and the residual oil then yielded 2.5 g. of product whichdistilled over at 96 C./ 80 mm. Hg. A total of 20.5 g. of

was obtained (69% yield). IR and NMR analysis confirmed the structure.

Analysis.Calc. for C H F O (percent): C, 29.04; H, 1.90; F, 56.16. Found(percent): C, 29.21; H, 1.91; F, 56.01.

EXAMPLES I AND J 6-perfluoroisopropoxy 1,1,2,2 tetrahydroperfluorohexylacetate, (CF CFO(CF CH CH 0OCCH and 8- perfiuoroisopropoxy 1,1,2,2tetrahydroperfluorooctyl acetate, 2CFO(CF2 GCH2CH2OOCCH3 (CE, CFO (CF CHCH OOCCH (I) employing the synthesis Example H.

method described in 14 EXAMPLES K, L AND M4-perfluoroalkyl-3-buten-l-ol, cis and trans,

R CH=CHCH CH OH (K), 6-perfluoroalkyl-3-oxa-5-hexen-1-ol, cis and trans,R CH=CHCH OCH CH 0H (L), 6 perfluoroalkyl-3-oxahexan 1 ol, RfCH CHgCHQCH CHgOH (M) (Percentage indicates area percentages as determined byVPC analysis).

is converted (a) into R CH=CHCH CH OH (K) employing the 2-step synthesisshown in Example A, and (b) into !R CH=CHCH OCH CH OH (L) employing the2- step synthesis shown in Example F, and (c) into R CH CH CH OCH CH OH(M) employing the catalytic hydrogenation method described in Example G.

EXAMPLE 1 Bis (4 -perfluoroispropoxy- 1 1,2,2-tetrahydroperfluor0-butyl) fumarate,

:[CH0 0 OOI'IgCHiC FzC F20 C F(C F92] trans 4-perfluoroisoprop oxy-l1,2,2-tetrahydroperfluorobutylacetate, 20.0 g., 0.054 mole (Example H),diethyl fumarate (3.62 g., 0.021 mole), para-toluene sulfonic acidmonohydrate (1.025 g., 0.0054 mole) were charged into a 3-neck flaskequipped with a nitrogen inlet, magnetic stirrer and a reflux regulatingdistillation head (Kontes K287600). While a slow stream of nitrogen waspassed through the system, the reactants were heated to C. for 2 hours;then the temperature was raised to C. and ethyl acetate slowly distilledover. Then, after 19 hours of heating, the temperature was raised to C.and maintained there for one hour while a slight vacuum (360 mm. Hg) waspulled. The reaction mixture was cooled, then triethylamine (1.6 g.,0.016 mole) was added to complex the p-toluene sulfonic acid. Themixture was then dis tilled and the product was obtained as a colorlessliquid (B.P. 110 C./0.2 mm. Hg) in a 75% yield (11.65 g.),

VPC showed the product to be pure. The NMR showed proton resonances at 62.47, 4 protons in triplets of a triplet (CF Q11 CH 2; 6 4.5, 4 protonsin a triplet, (CH (3 O) 2; 6 6.85, 2 protons .in a singlet -CHCOO)X 2Bis[4- (perfluoroheptyl)-3-butenyl] fumarate %CHCOOCHzCHzCH=CHU1F trans.2

4-perfluoroheptyl-3-buten-1-01 (20.4 g., 0.046 mole, Example A)spectrograde toluene (80 g.) and fumaryl chloride (3.48 g., 0.02275mole, distilled!) were charged into a 3-neck flask equipped with areflux condenser (protected by a drying tube), nitrogen inlet and amagnetic stirrer. The mixture was refluxed for 29 hours after which timeVPC analysis showed a conversion of 91%. The reaction mixture wascooled, and passed through a column containing neutral aluminum oxide(Alox, activity I) to remove unreacted acid chloride and fluoroalcohol.The column was washed with five portions of dry benzene (125 ml. each)and the solvent of the combined fractions was stripped off in a rotaryevaporator. The oily residue was distilled in a short path distillationapparatus, B.P. 182 C./0.4 mm., and 15.4 g. of a colorless oil wasobtained (70.6% yield), showing one single peak by VPC. The NMR showedproton resonances at 2.65, 4 protons, multiplets, -OQIi CH 5 4.25, 4protons, triplet -OCH Q I;I CH=; 6 5.15-6.68, 4 protons, multiplets, QH=Qg-C F 6 6.78, 2 protons, singlet,

These data are consistent for the above structure. Analysis.-Calc. for CH F O (percent): C, 32.51; H, 1.47; F, 59.35. Found (percent): C, 32.32;H, 1.50; F, 59.43.

EXAMPLE 3 Bis[4-(perfluoroheptyl)-3butenyl] itaconate,

4-perfluoroheptyl-3-buten-l-ol (16.0 g., 0.0362 mole, Example A),spectrograde toluene (70.0 g.) and itaconyl chloride 13.2 g., 0.0181mole, distilled were charged into a 3-neck flask which had been equippedwith a condenser (protected by a drying tube), nitrogen inlet and a magnetic stirrer. The reactants were refluxed for 40 hours after which timea VPC analysis showed a conversionof 87% to the diester. The cooledreaction mixture was then passed through a column containing neutralaluminum oxide (activity I) to remove unreacted alcohol and acidchloride. The product was washed from the column with 3-125 ml. portionsof benzene. The fractions were combined and the solvent was stripped offin a rotary film evaporator. The oily residue (13.4 g.) was distilled ina short path distillation apparatus and 8.4 g. of a pure product, B.P.ISO-181 C./0.5 mm., was obtained (48% yield). A VPC analysis showed onesingle peak. The NMR spectrum showed proton resonances at 6 2.1-3.2, 4protons overlapping multiplets, -CH Q I CH=CH-; 6 3.32, 2 protons,singlet, 9 g COOCH 6 4.0-4.5, 4 protons, complex multiplet, COOQ CH 55.4-7.0, 4 protons, complex multiplets, CH Q1=@CF 6 5.72 and 6 6.32, 2protons, apparent singlets, QH =O These data are consistent for theabove structure.

Analysis.-Calc. for C H F O (percent): C, 33.28; H, 1.66; F, 58.50.Found (percent): C, 33.31; H, 1.69;

EXAMPLE 4 Bis [4- (perfiuorobutyl) -3 -butenyl] fumarate:[CHCOOCHICHQCH=OHC(F9] 16 orator and the oily residue was distilled ina short path apparatus. The product (B.P. ISO-152 C./0.6 mm.; 17.3 g.)was obtained in 76% yield and was shown by VPC analysis to be pure. TheNMR spectrum showed proton resonances at 5 2.7, 4 protons, unresolvedmultiplet,

6 4.32, 4 protons, triplet, COOCH CH 6 5.2-6.6, 4 protons, complexmultiplets ;I :(lCF 6 6.82, 2 protons, singlet,

These data are consistent for the above structure. AnaIysis.-Calc. for CH F Q, (percent): C, 36.38; H, 2.14; F, 56.79. Found (percent): C,36.45; H, 2.23; F, 52.31.

EXAMPLE 5 Bis 1 1- (perfluoroheptyl)-10-undecen-1-yl] fumarate1l-perfluoroheptyl-IO-undecen-l-ol (20.0 g., 0.0372 mole, Example D)spectrograde toluene (80 g.) and fumaryl chloride (12.84 g., 0.0186mole, distilled) were refluxed as in Example 2. After 22 hours thereaction was complete as shown by VPC and IR analyses. The reactionmixture was cooled and then passed through a column of aluminum oxide(neutral, activity I). The product was washed from the column withfourml. portions of benzene. The wash fractions were combined and thesolvent was removed on a rotary film evaporator. The residue wascrystallized from petroleum ether. The purified product (white crystalsM.P. 36-37.5 C.) was obtained in a 54% yield (1.6 g.) A small sample ofthis was recrystallized 2 times from petroleum ether, M.P. 38-39 C. TheNMR spectrum showed proton resonances at 6 1.2-1.9, 28 protons, singletand broad multiplets 40119 6 1.9-2.55, 4 protons, broad, CH CH=CH; 54.20, 4 protons, triplet -Ofi CH 5 5.0-6.6, 4 protons, complex multilicity, -CH Q=G Il-CF 6 6.85, 2 protons, singlet,

These data are consistent for the above structure. Analysis.-Calc. for CH F O (percent): C, 41.53; H, 3.66; F, 49.28. Found (percent): C, 41.75;H, 3.63; F, 49.31.

EXAMPLE 6 Bis 1 1 -(perfluoroisopropyl) -10-undecen-1-yl] fumarate l1perfluoroisopropyl-lO-undecen-1-ol (21.0 g., 0.062 mole, Example E),spectrograde toluene (80 g.) and fumaryl chloride (4.52 g., 0.0295 mole,distilled) were refluxed as in Example 1. After 24 hours of reflux, thereaction Was complete as shown by VPC analysis. The toluene was strippedoff on a rotary film evaporator. The oily residue, 24 g., was distilledin a short path distillation apparatus. The product was obtained as acolorless oil (B.P. 228 C./0.5 mm.) in 78.5% yield (17.5 g). The NMRspectrum showed proton resonances at 6 1.1-2.4, 32 protons, singlet andcomplex multiplets,

propro- 17 tons, triplet of doublets, -@=CHCF; 6 6.8, 2 protons,singlet,

These data are consistent for the above structure. Analysis-Cale. for CH F O (percent): C, 50.79; H, 5.60; F, 35.15. Found (percent): C, 51.09;H, 5.54; F, 34.99.

EXAMPLE 7 Bis[6-(perfluoroheptyl)-3-oxa-5-hexen-1-yl]tumarate LE-CBC OOCHQCHZOCH1CH=CHC1F151 6-perfiuoroheptyl-3-oxa-5hexen-l-ol (22.0 g.,0.0467 mole, Example F), spectrograde toluene (80 g.) and fumarylchloride (3.26 g., 0.02125 mole, distilled) were refiuxed as in Example2. As indicated by VPC analysis, the reaction was complete after 14hours of reflux. The reaction mixture was cooled and then passed througha column of neutral aluminum oxide (activity I). The product was washedfrom the column with 350 ml. of benzene, and was then stripped ofsolvent on a rotary film evaporator. The liquid residue was distilled(B.P. 205- 206 C./0.4 mm.) in a short path distillation apparatus; 13.7g. of product was obtained (yield63%) which showed one peak by VPCanalysis. The NMR spectrum showed proton resonances at 5 3.75, 4protons, complex multiplet, COO%CH OCH 8 4.30, 8 protons, overlappingmultiplets, COOE CH OQ II 6 5.7- 6.8, 4 protons, complex CH QI I GECF 66.95, 2 protons, singlet,

:ECHCOO EXAMPLE 8 Bis [6- (perfluoroheptyl) -3-oxa-5-l1exane-1-yl]itaconate 6 perfiuorheptyl-3-oxa-5-hexen-1-01 (22.0 g., 0.0467 mole,Example F), spectrograde toluene (80 g.) and itaconyl chloride (3.55 g.,0.02125 mole, distilled) were refluxed, as in Example 1, for 48 hours atwhich time a VPC analysis showed a complete reaction. The reactionmixture was then passed through a column of neutral aluminum oxide(activity I). The product was washed from the column with 3X 125 ml.portion of benzene. The fractions were combined, and the sol-vent wasstripped off on a rotary film evaporator. The oily residue was distilled in a short path distillation apparatus yielding 8.4 g. (38%yield) of product (B.P. 208-216 C./0.8 mm.). The product yielded onesingle peak by VPC analysis. The NMR spectrum showed proton resonancesat 6 3.38, 2 protons in a singlet, =C(COO)CH COO; 6 3.5- 3.9, 4 protonsin unresolved multiplets, 2

CH CH OCH 5 3.954.7, 8 protons in unresolved multiplets, 2

COO C I- I CH O G Ii CH-= 6 5.65-7.0, 4 protons in complex overlappingmultiplcts 2X CH=CHCF 5 5.75 and 5 6.35, 2 protons in apparent singlets,C H =C These data are consistent for the above structure. Analysis.Calc.for C H F O (percent): C, 33.67; H, 1.95; F, 55.10. Found (percent): C,33.58; H, 1.95; P, 54.89.

1 8 EXAMPLE 9 Bis[6-(perfiuoroheptyl)-3-oxahex-l-yl]fumarate :[ono oocmomoomcmcmomn] 6 perfluoroheptyl 3-oxahexan-1-ol (19.0 g., 0.0402mole, Example G), spectrograde toluene g.) and fumaryl chloride (3.08g., 0.0201 mole, distilled) were refluxed, as in Example 2, for 30 hoursat which time a VPC check showed a complete reaction. The reactionmixture was cooled and then passed through a column of neutral aluminumoxide (activity I). The product was washed from the column with 500 ml.of benzene. The solvent was then stripped off on a rotary filmevaporator and the oily residue was distilled in a short pathdistillation apparatus yielding 12.5 g. (60.7% of theoretical yield) ofproduct (B.P. 202 C./0.4 mm.). The purified product showed one singlepeak by VPC analysis. The NMR spectrum showed protonresonances at 61.5-2.7, 8 protons in broad unresolved signals, 2X

These data are consistent for t h e 1563c structure.

Analysis.Calc. for C fi F O (percent): C, 32.83; H. 2.17; F, 55.64.Found (percent): C, 32.91; H, 2.15; F, 56.10.

EXAMPLE 10 l3is[6-(perfluoroheptyl)-3-oxal1ex-1-yl] itaconatecH,=qcoocmcmocmcmomqmg cit coocInclenocn crncrncn 6 perfluoroheptyl3-oxahex-an-1-ol (19.0 g., 0.0402 mole, Example G), spectrogradletoluene (80 g.) and itaconyl chloride (3.36 g., 0.0201 mole, distilled)were refluxed, as in Example 1, for 50 hours. A VPC check at this timeshowed a complete reaction. The reaction mix ture was cooled and thenpassed through a column of neutral aluminum oxide (activity I). Theproduct was washed from the column with 375 ml. of benzene which wasthen stripped off on a rotary film evaporator. The oily residue wasdistilled in a short path distillation apparatus yielding 10.7 g. (51.4%of theoretical yield) of product B.P. 183-187 C./.02 mm.). The productwas shown to be pure by VPC analysis. The NMR spectrum showed protonresonances at 5 1.45-2.85, 8 protons in broad unresolved multiplets, 2X(OCH C H,Q I I CF 6 3.32, 2 protons in a singlet, -'=C(COO)CH COO-; 63.2-4.1; 8 protons in overlapping multiplets, 2X

(CH CH OGH CH 6 40,-4.8, 4" protons in overlapping triplets, 2X

. QQHz D) EXAMPLES 11 TO 15 R acetates I and .l' and R -alcohols K, Land M were converted into cap-unsaturated diand triesters of type I aslisted in Table l by employing transesterification methods as describedin the previous Examples 1, 2 and 3.

TABLE 2-Cont1nued Elemental analyses, percent Mono- Composition ofmonomer mixture (Equlmolarratlo of Rr-monomer to mar comonomer) 7Appearance Yield, Calculated Found Ex.- Ex. of after No. No. Ry-MonomerComonomer copolymer. ppt. C H F C H 1 24.... 3 SameasExample23-. MVE'Sgihcolor- 68.94 34.90 215 55.21 34.37 2.06 56.25

ess: 25-..- 3 do STY Tough 85.85 38.97 2.24 52.85 39.80 2.39 50.65

F brittle. 26...; 4 ZLCHCOOCHICH1 DH=CHCIFQJ HBVE So11t,cclor- 93.540.22 3.58 44.05 40.47 3.32 45.09 a ass.

27....- 4 As above MVE Bolt, tough 91.31 38.45 2.80 47.60 38.77 2.8048.31

F polymer. 28--..- 5 LECHCOO(CH1)QOH=CHC1FIB] HBVE So1ft,color- 87.443.40 4.28 44.78 43.19 4.17 46.15

2 ass.

29...; 5 Asabove MVE Verysott 92.37 42.51 13.98 46.92 42.90 3.98 46.91 5do STY Tacky, 73.85 45.72 4.00 45.21 45.98 4.04 45.42

F viscous. 31---; 6 :LCHCOO(CH CH=CHCF(CF;)|] HBVE Viscous 011-- 78.452.29 0.24 30.48 52.02 6.02 32.77

32--..- 6 Asabove MVE Colorless, 83.61 51.59 5.94 32.65 53.89 6.34 32.75

' high vlscous. 33-...- 7 :rECHCOOCHaCH1OCH:CHrLCHC F HBVE Sinccolor-92.5 35.93 2.67 50.15 35.28 2.49 51 92 z ass.

34....- 7 Asabove MVE -.-.do 95.83 34.52 2.24 52.85 34.38 2.31 53.25 357 do STY Soft, tough 82.57 34.52 12.24 52.85 23.38 2.31 53.25

polymer.

36-..- 8 CH,=CCOCH;CH;OCH;CH=CHC1FH HBVE Soft, tacky 72.5 3653 2.8049.52 .-5002 HzCQOCH CH3OCHzCH=CHC1Fu 37---.- 8 As above -21.": MVE801th, eolor- 56.86 35.18 2.40 52.17 34.13 2.13 52.42

ess. 38--.; 9 :ECHCO0CH:CH:O(011:):01Fu] HBVE do 88.3 35.80 3.00 49.9734.56 2.67 50.75

39--.: o Asabove.-..-..-;.-.-.- MVE B0it,1taelry 93.54 3439 2.60 52.6523.01 2.63 53.38

poymer. 40 9 do BTY Bolt, tough 83.43 38.31 2.68 50.51 38.89 2.82 49.91

polymer.

41--.; 10 CH CHCOOCHzCHzOCHzCHzCHzC' Fn HBVE Boltt,eolor- 82.5 36.413.14 49.37 35.62 2.97 50.94

H eOOCHzCHzOCHzCHgCHaCIFu 42 1o Asabova MVE .do 70.92 35.05 2.76 51.983519-265 52.24 43 10 do STY Soft, tough" 84.54 38.89 2.82 49.88 40.892.35 48.91

\ EXAMPLES 44 AND 45 Ten parts of monomers Example 2 or 7 and 0.025 partof benzoyl peroxide were sealed in an ampul under nitrogen andpolymerized for 16 hours at 80 in a constant temperature oil bath. Theresulting polymer was dissolved in ten parts of hexafluoroxylene andthen precipitated into 200 parts of hexane under vigorous stirring. The

EXAMPLE 46 Employing the polymerization procedure described for Examples16 to 43, alternating copolymers of the novel R monomers Examples 11through 15 and thefollowing comonomers are prepared:

' methyl vinyl ether EXAMPLES 4749 "Pblynier' examples as listed inTable/3 were dissolved in hexafluoroxylene or Freon 113 and polymerfilms prepared by placing a few drops of the polymer solutions on aglass slide and with a clean edge spreading the solution over thesurface of the slide. Instantaneous solvent evaporation left the polymeras. a smooth film. Contact angles of octane to tetradecane on thepolymer films were measured using a Visco-Tech contact angle analyzer.From the contact angle data the critical surface tension v0 wasdetermined according to the following reference: W. Zisman, ContactAngles, Advances in Chemistry, No. 43, ACS Publications, Washington, DC,1964.

data obtained are listed in Table 3.

TABLE 3 Composition of alternating 1:1 copolymers Example Polymer -ycnumber Ex. N o. Rr-rnonomer Comonomer (dynes cm.)

17 Fumerete o1 (CF;)ICFOCF,CF1CH1CH,OH CH=CHOCHi 13.6 21 Fnmarate oiC1FHCH=CHCHZCH1OH As above 14. 1 22 d C 13.4 24 Iteeonate o1C1F1$CH=CHCHzCHzOH.. 12,1 27 Fumerete oi C4FaCH=CHCHzCH=OH As above 15.929 Fumerate o! C1F15CH=CH(CH:)9OH 17. 2 32 Furnarete01(CF;)CFCH=CH(CH,)OH 20.0 34 Fumerate o1C1FuCH=CHCH OCHCH1OH .do 13.135 do CHI=CHCQH 13.4 37 Itaeonete or C7F15CH=CHCH1OCH1CH1OH CH=CHOCH|12.1 39 Fumarete o1 C1F1s(CHz):OCHzCH;OH As above 15.8 40 d0 ACH1=CHC5H5 13.2 42 Iteoonete of C1FH CHQ=OCH1CH1OH CHQ=CHOCHI 14.4

EXAMPLES 60 TO 82 Homo and copolymers as listed in Tables 4 and 5 weredissolved in hexafiuoroxylene so that solutions with a 2% 0 0 solidcontent were obtained. These polymer solutionsEXCDFWCECHCMHMOJLVmxcpmcmmmocnmnollfi or were further diluted withmethyl chloroform and applied 20 alone or in combination with a polyisobutyl methacrylate extender to a polyester-cotton (65/35) fabric bypadding in such a way that 0.2% fluorine was deposited onto the mY is CF test fabric. After drying the test fabric at 150 c. for 3 q is 6 3?minutes, oil repellencies (AATCC and 3-M Oil Test) 25 m'iszto and'waterrepellencies (AATCC) were determined and 2 t data obtained as listed inTable 4 and 5. n o

TABLE 4 Repellency with 0.2% fluorine on PE Copolymers ofRi-monomeriiargd comonomers (equimolar AATCC/3-M oil AATCC water ra osPolymer No No Ex. No. Iii-monomer Comonomer l extender Extended lextender Extended l 16 Fumarate of (CFOzCFOCFzCFzCHzCHaOH- HBVE 5 4 7070 17 dn MVE 3 3 70 70 18 do VA 4 3 70-80 70 19 -do STY 3 3 70 70-80 20Fumarate of C FHCH=CHCHZCH1OH HBVE 4 4 70 70 21 do E 4 4 70 70-80 22 -doSTY 4 4 70 70-80 23 Iteeonate of C1F15CH=CHCH2CH2OH HBVE 2 3 70 70 24 dnMVE 2 2 70 70 25 do STY 2 3 70 70-80 33 Fnmarete of C F15CH=CHCHOCHCHzOH- HBVE 4 4 70 70 34 ;'--d0 MVE e 3 3 70-80 70 35 do STY 3-4 4 7070-80 36 ItnconateofC F15CH=CHCHzOCHzCHzOH HBVE 3 3 70-80 70-80 37 doMVE 2 2 70 70 38 Fumarate 0fC7F15CH1CH1CH1OCH1CH2OH- HBVE 4 4 70 70 39dn MVE 3 3 70-80 70-80 40 do STY H 4 70 70-80 41 Itaeonate 0tC1F15CH1CH2CHOCH;CH,OH- HBVE 2 3 70 70 42 dn MVE 2 3 70 70 43 dn STY- 33-4 70-80 70-80 1 HBVE=Hydroxy butyl vinyl ether; MVE=Methy1 vinylether; VA =Vinyl acetate; STY==styrene. Extended with polyisobutylmethacrylete to 20% fluorine in total sohds. I v

TABLE 5 Repellency with 0.2% fluorine on PE AATCC/EX M 011 AA'ICC waterPolymer No No Example number Ex. No. Homopolymer (o1igomer)o1- extenderExtended l extender Extended 81 44 Fumarete of C1FnCH=CHCHzCH1OH.--. a r3 1H0 70-80 82 Fumarete o! C1FuCH=CHCHzOCHzCHzO 3 3 70-30 1 Extended asin Table 4.

What is claimed p is 2 to 6 or zero; and 1. A compound of the formula: X15 oxygen or zero If p 18 zero 2. A compound of the formula: RIA R 70 maR 31 RI C=C wherein R R, R are hydrogen, methyl, R,A or R ACH with theproviso that at least one of R R, R repwherein resent R A or R;ACH R R Rare hydrogen, methyl, R A or R ACH a 25 p with the proviso that at leastone of R ,R R represent R A or R AcH r R A is Rg is C l q is 3 to 18; mis 1 to 12; n is 2 to 12; p is 2 to 6 or zero; and X is oxygen. I 3. Acompound of the formula:

wherein R, R, R are hydrogen, methyl, R,A or R,ACH

with the proviso that at least one of R R, R represent R;A or R,ACH R1is O RrXC FnCH=C HC-HmOC-Ha Rf is c Fg q is 6 to 12; m is 2 to 4; n is 2to 4; p is 2 to 6 or zero; and X is oxygen or zero if p is zero. 5. Thecompound of claim 1 wherein R and R are hydrogen and R is R,A-.

6. The compound of claim 4 wherein n is 2-4 and m is 2-4.

7. The compound of claim 5 wherein X is oxygen. 8. The compound of claim6 wherein X is oxygen. 9. The compound of claim 5 wherein p is zero andX is zero.

10. The compound of claim 6 wherein p is zero and X is zero.

11. Hompolymeis having water and oil repellency properties comprising askeletal chain with repeating units 9 h ermv FE! E Ll. izni wherein R RR are hydrogen, methyl, R,A or R,ACH

' with the proviso that at least one of R R R represent R' A or R ACH rAs q is 6-12;

mis 2-4;

It is 2-4;

, p is 6 or zero;

X is oxygen if p is zero.

12. Homopolymers having water and oil repellency properties comprising askeletal chain with repeating units of the formula:

I" 21A i Li's tel wherein R R, R are hydrogen, methyl, R A or R ACH withthe proviso that at least one of R R R represent R,A or R ACH RA is R!is C Fg j q is 3 to 18; mis 1 to 12; n is 2 to 12; p is 2 to 6 or zero;and X is oxygen. 13. Homopolymers having water and oil repellencyproperties comprising a skeletal chain with repeating units of theformula:

Pt 11 L 1' h] wherein R R R are hydrogen, methyl, 11A or R ACH with theproviso that at least one of R R, R represents R,A or R ACH RIA is R! isC Fz +fi q is 3 to 18; m is l to 12; n is 2 to 12; p is zero; X is zero.14. The homopolymer of claim 11 wherein R and R are hydrogen and R is RA.

15. The homopolymer of claim 11 wherein R and R are hydrogen and R isR;ACH;;.

16. The homopolymer of claim 14 wherein X is oxy- -17. The homopolymerof claim 15 wherein X is oxygen.

18. The homopolymer of claim 14 wherein p is zero and X is zero.

19. The homopolymer of claim 15 wherein p is zero and X is zero.

20. Copolymers of ethylenically unsaturated mon mers and the monomers ofclaim 1 having water and oil repellency properties.

21. Copoly-mers of ethylenically unsaturated monomers and the monomersof claim 2 having water and oil repellency properties.

22. Copolymers of ethylenically unsaturated monomers and the monomers ofclaim 3 having water and oil repellency properties.

23. A solid substrate containing a coating of the homopolymer of claim11.

24. The coated substrate of claim 23 which includes a textile.

25. A solid substrate containing a coating of the homopolymer of claim12.

28 26. A solid substrate containing a coating of the homopolymer ofclaim 13.

References Cited UNITED STATES PATENTS Domba Q. 26078.4

JOSEPH L. SCHOFER, Primary Examiner J. KIGHT III, Assistant Examiner US.Cl. X.R.

117-132 CF, 161 UC, UB; 26078.5 B, E, 79.7, 455 R, 485 F

